CN110124531A - A kind of porous carbon-Carbon-nanotube hollow fiber membrane preparation method can produce hydroxyl radical free radical under electrochemically strengthening effect - Google Patents
A kind of porous carbon-Carbon-nanotube hollow fiber membrane preparation method can produce hydroxyl radical free radical under electrochemically strengthening effect Download PDFInfo
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Abstract
The invention belongs to nanomaterial assembly technical fields, are related to a kind of porous carbon-Carbon-nanotube hollow fiber membrane preparation method that can produce hydroxyl radical free radical under electrochemically strengthening effect.It is characterized in that, the preparation method being related to is through the following steps that realize: the first step prepares the presoma Zif-8 of porous carbon；Second step prepares porous carbon；Carbon nanotube is acidified by third step in concentrated acid solution, introduces hydrophilic radical；4th step forms uniformly mixed spinning solution；5th step, wet spinning form hollow-fibre membrane.6th step and the 7th step are respectively to remove organic solvent and PVB, form target material.The advantage is that: preparation process is simple, without expensive equipment, method is flexibly controllable.Pass through O in the case where electricity helps2Reduction generate H2O2, then, H2O2With Fe2+Coupling generate OH free radical.OH free radical is used for degradation of contaminant, Fe3+It is Fe by electric assisted Reduction2+.Therefore, Fe2+/Fe3+Realize effective circulation.
Description
Technical field
The present invention relates to a kind of to can produce porous carbon-carbon nanotube of hydroxyl radical free radical under the action of electrochemically strengthening
The preparation method of hollow-fibre membrane belongs to nanomaterial assembly technical field.
Background technique
Membrane pollution problem is that the major technique of membrane separation technique hinders, and significantly limits the application of membrane separation technique.It is all
The schemes for alleviating fouling membrane are proposed more successively by numerous researchers, wherein electrochemical techniques can be stablized with it, efficient to remove
The polluter on membrane material surface and be concerned.Electrochemistry repulsive interaction can repel the polluter with identical charges, make it
Far from membrane material surface.Electrochemical oxidation process can be with the pollutant on the oxidation removal membrane material surface of non-selectivity and inside
Matter.And OH, O generated by power-up mode2 ·-、HO2Isoreactivity species can convert pollutant to low toxicity or nontoxic
Substance completely removes its mineralising to realize.
Carbon is a kind of element of earth rich content, its valence shell structure is 2s22p2, obtain electronics and betatopic not
It is easy, usually electronics is energized on p track from s track, with sp, sp2、sp3Three kinds of hybridized orbit form bondings, exactly by
In different bonding forms, carbon material is many kinds of and nature difference is larger, mainly includes than more typical carbon material electrode, stone
Ink, graphene (GR), porous carbon, carbon nanotube (CNT) etc..Wherein, porous carbon materials have big specific surface area, hole abundant
Gap structure, the complicated multiplicity of cellular structure, forming membrane material, especially hollow-fibre membrane using porous carbon, (hollow structure compares table
Area is big, and occupied area is small compared with other membrane material forms) be used as electrode material when can realize electroxidation technology, pass through pollution
OH, O that object and membrane material electrode directly occur electron transmission or generate with indirect electrooxidation2 ·-、HO2 ·Isoreactivity species are anti-
Pollutant should be converted to low toxicity or nontoxic substance, the realization of pollutant mineralising is completely removed.Alleviation fouling membrane is realized, is dropped
Solve pollutant and the regenerated triple targets of membrane material.But porous carbon is mostly graininess, and skeleton, mechanical strength cannot be formed after calcining
It is low, it is unfavorable for practical application.
Summary of the invention
Proposed adoption carbon nanotube of the present invention is as basic support frame, and using porous carbon as the main body of membrane material, preparation is new
The porous carbon hollow-fibre membrane of type.Preparation method proposed by the invention, simple process, without expensive equipment, method is flexible
Controllably, porous carbon-Carbon-nanotube hollow fiber membrane novel under electrochemically strengthening effect can produce hydroxyl radical free radical.
Basic conception of the invention is that the carbon nanotube of acidification and porous carbon are obtained structure using wet spinning technology is equal
One porous carbon-Carbon-nanotube hollow fiber membrane.
A kind of porous carbon-carbon nanotube can produce hydroxyl radical free radical under electrochemically strengthening effect proposed by the invention
The method and step of the preparation method of hollow-fibre membrane, preparation is as follows:
(1) presoma (zeolite imidazole ester skeleton) the Zif-8 preparation of porous carbon: by the methanol solution of zinc nitrate, with 2- first
After the mixing of the methanol solution of base imidazoles and triethylamine, 4 hours or more are stood again within ultrasound 30 minutes or more, carry out solid-liquid point later
From obtained solid is Zif-8 nanometer sheet.
The proportionate relationship of zinc nitrate and methanol is 7.435g:500ml in the methanol solution of the zinc nitrate；The 2- methyl
The proportionate relationship of 2-methylimidazole, triethylamine and methanol is 2.052g:3.2675g in the methanol solution of imidazoles and triethylamine:
500ml；The volume ratio of the methanol solution of the methanol solution and 2-methylimidazole and triethylamine of zinc nitrate is 1:1.
(2) prepared by porous carbon: the Zif-8 that step (1) obtains is placed in H2And N2In gaseous mixture, 2 are calcined at 800-1200 DEG C
Hour or more, it is cooled to room temperature.
(3) carbon nanotube is acidified: carbon nanotube being immersed in the mix acid liquor of concentrated nitric acid and the concentrated sulfuric acid, at 40~80 DEG C
Lower heat preservation 2~6 hours, is washed to neutrality, then be separated by solid-liquid separation later, and obtained solid is the carbon nanotube of acidification.Carbon nanometer
Pipe acidification is to introduce hydrophilic radical.
(4) prepare spinning solution: by step (2) resulting porous carbon, the carbon nanotube of step (3) resulting acidification and has
Solvent and PVB are mixed into uniform spinning solution.
The porous carbon and the mass ratio of the carbon nanotube of acidification are 1:1:1-4:1:1, the dosage of the organic solvent without
Particularly severe requirement, can be complete by stock dispersion.
(5) wet spinning: spinning solution obtained in step (4) is flowed with coaxial spinning sandwich layer spinning solution with 1:1-2:1
Speed is injected into coagulating bath through coaxial spinning nozzle, is carried out wet spinning, is obtained Hollow-fibre membranes material.
The coaxial spinning sandwich layer spinning solution is water, and coagulating bath is water.
Specifically, preparing membrane material using Coaxial nozzle, wherein spinning solution is by the outer wall of Coaxial nozzle, and water is as core
Layer spinning liquid passes through the centre of axis spray head, and the material of formation is directly immersed in water.
(6) it removes organic solvent: the Hollow-fibre membranes material that step (5) are formed being impregnated 10-14 hours in water, makes to have
Solvent is fully dissolved out, then by formed membrane material naturally dry.
(7) anaerobic is calcined: under oxygen free condition, the Hollow-fibre membranes material that step (6) obtains being calcined in 500-700 DEG C
It 0.5-4 hours, is cooled to room temperature later, removes PVB, obtain porous carbon-Carbon-nanotube hollow fiber membrane.
In the present invention, it is preferred that zinc nitrate described in step (1) is zinc nitrate hexahydrate.
In the present invention, it is preferred that the method that Zif-8 described in step (1) is separated by solid-liquid separation is vacuum filtration and high speed centrifugation
One of.
In the present invention, it is preferred that the preparation of porous carbon in step (2): the Zif-8 that step (1) obtains is placed in H2And N2It is mixed
It closes in gas, calcined 2 hours at 1000 DEG C or more, it is cooled to room temperature.
In the present invention, it is preferred that the volume of concentrated nitric acid and the concentrated sulfuric acid is 1:3~5 in mix acid liquor described in step (3).
In the present invention, it is preferred that carbon nanotube solid-liquid separating method described in step (3) is vacuum filtration and high speed centrifugation
One of.
In the present invention, it is preferred that organic solvent described in step (4) is n,N-Dimethylformamide (DMF), and dimethyl is sub-
Sulfone etc..
In the present invention, it is preferred that remove organic solvent in step (6): the Hollow-fibre membranes material that step (5) are formed in
It is impregnated 12 hours in water, is fully dissolved out organic solvent, then by formed membrane material naturally dry.
In the present invention, it is preferred that oxygen free condition described in step (7) is vacuum or inert gas shielding (such as nitrogen, argon gas
Deng).
In the present invention, it is preferred that anaerobic is calcined in step (7): under oxygen free condition, by hollow fibre obtained in step (6)
Dimension membrane material is calcined 0.5-4 hours in 600 DEG C, is cooled to room temperature later, removes PVB, it is hollow to obtain porous carbon-carbon nanotube
Tunica fibrosa.
It can produce hydroxyl radical free radical under electrochemically strengthening effect the invention further relates to the preparation of the Sustainable use above method
Porous carbon-Carbon-nanotube hollow fiber membrane.
Since carbon nanotube is because of its good electric conductivity, mechanical strength, higher specific surface area, unique chemical stability
And it is widely studied.Therefore, the present invention is made by introducing carbon nanotube in porous carbon using the support of carbon nanotube skeleton
With can successfully prepare the novel porous carbon-to-carbon nanotube hollow-fibre membrane with excellent electrochemical redox ability.
Main advantages of the present invention and beneficial effect are: preparation process is simple, without expensive equipment；Method is flexible, system
Standby porous carbon-Carbon-nanotube hollow fiber membrane structure-controllable；The porous carbon of preparation-Carbon-nanotube hollow fiber membrane main structure
Beauty, it is well-balanced.
Detailed description of the invention
Fig. 1 is the preparation process explanation that the present invention is designed into.
The spinning solution of Fig. 1 (a) preparation；(b) spinneret used in；(c) spinning single unit system；(d, e) is prepared porous
Carbon-to-carbon nanotube hollow-fibre membrane.
Spinning solution is put into syringe, is put into another syringe with coaxial spinning sandwich layer spinning solution, with certain
Flow velocity is injected into coagulating bath through coaxial spinning nozzle, is carried out wet spinning, is obtained Hollow-fibre membranes material.Wherein, coaxial to spin
Silk sandwich layer spinning solution is water, and coagulating bath is water.
Fig. 2 be using the present invention relates to 1 porous carbon-Carbon-nanotube hollow fiber membrane scanning preparing of technology
Electron microscopic picture.
These scanning electron microscopic picture are using Hitachi S-4800 type scanning electron microscope, in the condition that acceleration voltage is 10kV
Lower shooting.
Fig. 3 is under different voltages, and porous carbon-Carbon-nanotube hollow fiber membrane is in electrochemically strengthening prepared by embodiment 1
Effect is lower to generate H2O2The case where.
Fig. 4 is that porous carbon-Carbon-nanotube hollow fiber membrane prepared by embodiment 1 generates hydroxyl under electrochemically strengthening effect
The spectrogram of free radical.
Fig. 5 is that porous carbon-Carbon-nanotube hollow fiber membrane prepared by embodiment 1 removes (a) under electrochemically strengthening effect
Phenol；(b) glucose；(c) effect of bovine serum albumin.
Fig. 6 porous carbon-Carbon-nanotube hollow fiber membrane pollution degradation substance mechanism explanation figure.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1
Porous carbon-Carbon-nanotube hollow fiber membrane the preparation method is as follows:
It is poured into 500ml methanol step 1: weighing 7.4350g zinc nitrate hexahydrate；Separately weigh 2.0520g 2- methyl miaow
Azoles and 3.2675g triethylamine are dissolved in new 500ml methanol, after its respectively ultrasonic dissolution, are mixed rapidly.After mixing
Solution continue ultrasound 30min after, mixing standing 4 hours, to obtain the nanometer sheet of 2 dimensions.Suction filtration is dried to obtain required Zif-8.
Step 2: weighing the Zif-8 of certain mass (2-4g) in tube furnace, to 1000 DEG C, calcining 2 is small for temperature programming
When, protection gas is H2And N2Gaseous mixture (volume ratio 1:1) is cooled to room temperature to get required porous carbon is arrived after calcining.
Step 3: the mix acid liquor (volume ratio 1:3) that 1g carbon nanotube is placed in concentrated nitric acid and the concentrated sulfuric acid is inner, it is heated to 60
DEG C, keep the temperature 3 hours.Then the mixed solution of concentrated nitric acid and the concentrated sulfuric acid is diluted with water, is washed to neutrality, carbon nanotube is passed through
Vacuum filtration is separated.
Step 4: weighing 0.5g porous carbon, 0.5g carbon nanotube, 0.5g PVB is dissolved in 12ml n,N-Dimethylformamide
In solution, stirring and dissolving 6h or more obtains uniformly mixed spinning solution.
Step 5: being packed into spinning solution using 20ml syringe, another 20ml syringe is packed into clear water, and connection is coaxial
Spray head (outer diameter 1.5mm, internal diameter 0.7mm), wherein spinning solution is passed through in axis spray head by the outer wall of Coaxial nozzle, water
Between, the flow velocity of spinning solution and water is respectively the material that 24ml/h and 12ml/h is formed, and is directly immersed in water and solidifies, obtains membrane material
Material.
Step 6: the membrane material of formation is impregnated 12 hours in water, it is fully dissolved out organic solvent.Then, by institute's shape
At membrane material naturally dry.
Step 7: being under conditions of protecting gas, membrane material to be calcined 0.5-4 hours in 600 DEG C, is cooled down later with nitrogen
To room temperature, porous carbon-Carbon-nanotube hollow fiber membrane is obtained.
It is learnt by Fig. 2, porous carbon-Carbon-nanotube hollow fiber membrane prepared by the present embodiment has uniform inside/outside diameter
(500/850 μm), and the porous carbon laminated structure that success visible in detail is adulterated in figure 2 c, the tubular structure of carbon nanotube
Play good supporting role.
Embodiment 2
Utilize the patent application of publication number CN109384307A: one kind is with electrochemically strengthening Carbon-nanotube hollow fiber membrane
The building principle of the membrane bioreactor of separative unit builds experiment filter device, will be in the carbon nanotube in membrane bioreactor
Empty fiber membrane replaces with porous carbon-Carbon-nanotube hollow fiber membrane prepared by 1 method of embodiment, as anode, titanium net conduct
Cathode, and the experiment filter device is not needed using activated sludge, other component and the equal reference of connection relationship in device
CN109384307A.Wherein, testing porous carbon-Carbon-nanotube hollow fiber membrane component in filter device is that 6 porous carbon-to-carbons are received
Mitron hollow-fibre membrane is connected in parallel the membrane module to be formed, and porous carbon-Carbon-nanotube hollow fiber membrane connects power supply as cathode
Cathode, and effective area be 5.44 × 10-4m2；Using the titanium net 12 of 10cm × 10cm as anode, the anode of power supply is connected, by
This constitutes closed circuit, in cathode and anode applied voltage.Porous carbon-Carbon-nanotube hollow fiber membrane component outer wall and titanium net
Inner wall is spaced about 3mm.Embodiment 3-4 completes test in the filter device.
Different voltages strengthen porous carbon-Carbon-nanotube hollow fiber membrane hydrogen peroxide generation prepared by lower embodiment 1:
In membrane separating process, OH is to pass through H2O2(electricity-Fenton's reaction) decomposes acquisition.Therefore, H2O2Generation
It is played a crucial role during OH is generated.Electrochemically strengthening membrane material generates H in the present invention2O2It is biasing selected
For -0.6V, -0.8V and -1.0V, reaction system is the acid solution for being 3 with the pH value of sulfuric acid tune.As shown in figure 3, working as O2In carbon
When electrochemical reduction occurring on nanotube-porous carbon hollow-fibre membrane, obtained in the voltage range of -0.6~-1.0V
21.45~40.01 μm of olL-1H2O2Yield.In addition, Fig. 3 is shown in H under the application voltage of -1.0V2O2Generation with-
0.8V is compared to slightly higher, it is contemplated that energy conservation, unless otherwise stated, following experiment is carried out at -0.8V.
Embodiment 3
Using the filter device of embodiment 2, test in porous carbon-carbon nanotube prepared by electrochemically strengthening embodiment 1
The generation of hydroxyl radical free radical under the action of empty fiber membrane:
Exposed in system under sufficient dissolved oxygen conditions, investigate respectively iron ion (0.2mM, from ferrous sulfate) and
Whether it is powered on and hydroxyl radical free radical is had an impact.As a result as shown in figure 4, in electricity auxiliary (- 0.8V) porous carbon-carbon nanotube
There is intensity than four peak-to-peak signals for 1:2:2:1 in empty fiber membrane, this is similar to typical free radical spin adduct.Together
When, that, without there is typical peak signal, this does not show auxiliary in electricity in porous carbon-Carbon-nanotube hollow fiber membrane of electricity auxiliary
It helps down and produces OH.In addition, in no Fe2+In the case where, electric auxiliary porous carbon-to-carbon nanotube hollow-fibre membrane is not also found
DMPO-OH adduct signal, shows H2O2It cannot be in no Fe2+It is changed into OH in the case where ion.
Embodiment 4
Using the filter device of embodiment 2, porous carbon-Carbon-nanotube hollow fiber membrane prepared by testing example 1 is in electricity
Chemical strengthening acts on the effect for the depollution substance that goes down:
Fig. 5 a-c is shown removes phenol at different conditions, glucose and bovine serum albumin as a result, wherein phenol, Portugal
The concentration of grape sugar and bovine serum albumin is 50mg/L, and the concentration of iron ion (from ferrous sulfate) is 0.2mM.In no electricity
In the case where helping, porous carbon-Carbon-nanotube hollow fiber membrane shows lower phenol removal rate (8.6%).Due to phenol point
Much smaller size of the son relative to fenestra, therefore cannot be removed by porous carbon-Carbon-nanotube hollow fiber membrane crown_interception
Phenol.In -0.8V, porous carbon-Carbon-nanotube hollow fiber membrane is in Fe2+It can remove about 83.5% phenol under existence condition,
This is approximately 9.7 times of independent film filtering.The high removal rate of electric auxiliary porous carbon-to-carbon nanotube hollow-fibre membrane Pyrogentisinic Acid is initially returned
Because power in film surface-Fenton's reaction efficiently produces OH.Be free of Fe2+, there are under electric aided case, porous carbon-to-carbon nanometer
Pipe hollow-fibre membrane removes the phenol removal that phenol only obtains 9.2%, this is attributable to the adsorption effect of material.
Fig. 5 b illustrates porous carbon-Carbon-nanotube hollow fiber membrane to glucose removal effect.Pass through porous carbon-to-carbon nanometer
Pipe hollow-fibre membrane contains Fe under -0.8V effect2+When (0.2mM), to the removal rate about 65.4% of glucose, do not have about
6.2 times under electric subsidiary conditions.In addition, under identical voltage, without Fe2+Electric auxiliary porous carbon-to-carbon nanotube doughnut
Film removes only 12.8% glucose.
Fig. 5 c illustrates that porous carbon-Carbon-nanotube hollow fiber membrane goes division result to protein.It can be found that electricity auxiliary
Porous carbon-Carbon-nanotube hollow fiber membrane is in Fe2+It is about 89.2% to the removal efficiency of bovine serum albumin under the conditions of depositing, is approximately only
Contain Fe2+Only under electric aided case, to 2.7 and 2.3 times of the removal rate of protein.
Fig. 6 illustrates to pass through O in the case where electricity helps2Reduction generate H2O2, then, H2O2And Fe2+Become Fe3+Certainly with OH
By base.H2O2With Fe2+It is coupled the OH free radical generated, is used for degradation of contaminant, Fe3+It is Fe by electric assisted Reduction2+.Cause
This, Fe2+/Fe3+Realize effective circulation.
Above embodiments show that porous carbon-Carbon-nanotube hollow fiber membrane novel in the present invention is made in electrochemically strengthening
Under, in Fe2+In the presence of can produce OH, OH improves membrane material to the removal effect of polluter.
Claims (9)
1. a kind of porous carbon-Carbon-nanotube hollow fiber membrane preparation that can produce hydroxyl radical free radical under electrochemically strengthening effect
Method, which comprises the following steps:
(1) prepared by Zif-8: after the methanol solution of zinc nitrate is mixed with the methanol solution of 2-methylimidazole and triethylamine, ultrasound
4 hours or more are stood again within 30 minutes or more, be separated by solid-liquid separation later, obtained solid Zif-8；
The proportionate relationship of zinc nitrate and methanol is 7.435g:500ml in the methanol solution of the zinc nitrate；The 2-methylimidazole
Proportionate relationship with 2-methylimidazole, triethylamine and methanol in the methanol solution of triethylamine is 2.052g:3.2675g:500ml；
The volume ratio of the methanol solution of the methanol solution and 2-methylimidazole and triethylamine of zinc nitrate is 1:1；
(2) prepared by porous carbon: the Zif-8 that step (1) obtains is placed in H2And N2In gaseous mixture, calcined 2 hours at 800-1200 DEG C
More than, it is cooled to room temperature；
(3) carbon nanotube is acidified: carbon nanotube being immersed in the mix acid liquor of concentrated nitric acid and the concentrated sulfuric acid, is protected at 40~80 DEG C
Temperature 2~6 hours, is washed to neutrality, then be separated by solid-liquid separation later, and obtained solid is the carbon nanotube of acidification；
(4) prepare spinning solution: by step (2) resulting porous carbon, the carbon nanotube of step (3) resulting acidification is and organic
Solvent and PVB are mixed into uniform spinning solution；
The porous carbon, the carbon nanotube of acidification, PVB mass ratio be 1:1:1-4:1:1；
(5) wet spinning: by spinning solution obtained in step (4), with coaxial spinning sandwich layer spinning solution with the flow velocity of 1:1-2:1
It through coaxial spinning nozzle, is injected into coagulating bath, carries out wet spinning, obtain Hollow-fibre membranes material；
The coaxial spinning sandwich layer spinning solution is water, and coagulating bath is water；
(6) it removes organic solvent: the Hollow-fibre membranes material that step (5) obtains being impregnated 10-14 hours in water, then will be hollow
Fiber film material naturally dry；
(7) anaerobic is calcined: under oxygen free condition, the Hollow-fibre membranes material that step (6) obtains being calcined 0.5- in 500-700 DEG C
It 4 hours, is cooled to room temperature later, obtains porous carbon-Carbon-nanotube hollow fiber membrane.
2. preparation method according to claim 1, which is characterized in that zinc nitrate described in step (1) is six nitric hydrates
Zinc.
3. preparation method according to claim 1, which is characterized in that organic solvent described in step (4) is N, N- diformazan
Base formamide or dimethyl sulfoxide.
4. preparation method according to claim 1, which is characterized in that in mix acid liquor described in step (3) concentrated nitric acid and
The volume of the concentrated sulfuric acid is 1:3~5.
5. preparation method according to claim 1, which is characterized in that the method for separation of solid and liquid described in step (1) is vacuum
One of suction filtration and high speed centrifugation.
6. preparation method according to claim 1, which is characterized in that the method for separation of solid and liquid described in step (3) is true
One of empty pump filter and high speed centrifugation.
7. preparation method according to claim 1, which is characterized in that oxygen free condition described in step (7) is vacuum or lazy
Property gas shield.
8. preparation method according to claim 7, which is characterized in that the inert gas is nitrogen or argon gas.
9. the preparation of method described in any one of claim 1-8 can produce hydroxyl radical free radical under electrochemically strengthening effect
Porous carbon-Carbon-nanotube hollow fiber membrane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113600034A (en) * | 2021-08-30 | 2021-11-05 | 大连海事大学 | Preparation method of titanium suboxide hollow fiber membrane |
| CN116024601A (en) * | 2022-12-28 | 2023-04-28 | 大连理工大学 | Carbon nano tube-based porous hollow fiber electrode for electrocatalytic reduction reaction and application |
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